Mater. Res. Soc. Symp. Proc. Vol. 901E © 2006 Materials Research Society 0901-Ra16-55-Rb16-55.

Novel Synthesis of Gold Nanoparticles in Aqueous Media

A. Sugunan and J. Dutta

Microelectronics, School of Engineering and Technology,
Asian Institute of Technology, Pathumthani, 12120, Thailand

ABSTRACT

Aqueous synthesis of glutamate functionalized single crystal gold nanoparticles was achieved by
reducing a solution of chloroauric acid with monosodium glutamate. Highly uniform size
distributions of the nanoparticles can be obtained by having an excess of monosodium glutamate
in the starting solution. Similar to the conventional synthesis of gold nanoparticles by reduction
of chloroauric acid with trisodium citrate, the obtained particle sizes were varied in the range of
14 – 25 nm without loosing the uniformity in its size distribution by varying the concentration of
the reducing agent.

INTRODUCTION

Colloidal gold nanoparticles have been studied for over 100 years, mostly directed towards a
better understanding of their physical and chemical properties like surface plasmon absorption
and catalytic activities [1]. The ‘near monodisperse’ size distribution of the particles of these
colloids was of special interest in order to test various theoretical models of colloidal stability
and acquire knowledge on the nature of particle agglomeration process [2], self assembly of
colloidal particles in two dimensional or more complex three dimensional (3D) superstructures
[3], amongst others. In recent years, application of colloidal gold nanoparticles as sensors for a
wide variety of analytes, like heavy metal cations [4] and biological molecules [5] has attracted a
renewed attention from researchers. One of the most widely used precipitation methods for the
synthesis of gold colloids , proposed by Turkevich, in water involves the reduction of an aqueous
solution of chloroauric acid (HAuCl4) by trisodium citrate [1,6]. These nanoparticles are known
to be stabilized by a physical adsorption of excess citrate ions from the medium [6].
For most biological applications like bio-sensors and novel assemblies based of biological
structures, use of conventional gold nanoparticles involves an additional step of ligand exchange
with a bio-molecule that often leads to de-stabilization of the colloidal suspension. This can be
avoided by employing bio-available molecules like acidic amino acids to reduce chloroauric acid
to form gold nanoparticles with bio-compatible surface properties. Successful attempts to use
amino acids as a reducing agent for chloroauric acid have been reported for aspartic acid [7]. To
the best of our knowledge this is the first report on the precipitation and characterization of gold
nanoparticles utilizing the amino acid derivative, monosodium glutamate (MSG). Morphology,
crystallinity and surface properties of the synthesized gold nanoparticles obtained at varying
experimental conditions are presented and discussed.
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EXPERIMENTAL DETAILS

Stock solutions of 5 mM chloroauric acid (Sigma-Aldrich) in de-ionized water (Solution A) and

25 mM monosodium glutamate (Sigma-Aldrich) in deionised water (Solution B) was prepared in
clean and dry glass bottles.
Synthesis of glutamate stabilized gold nanoparticles: In 50 ml of de-ionized water, 2 ml of
Solution A was added and the mixture was heated till boiling. Upon boiling, aliquots of solution
B (such that the molar concentration ratio of monosodium glutamate to chloroauric acid was
adjusted to 7, 6, 5, 4, 3, and 2 following our experimental design), was added to this mixture and
heating was continued at boiling conditions. The color changes variably according to the specific
molar ratio used in the synthesis. In general, when the color of the colloid stabilized (no change
in visible color for over 60 sec), it was rapidly quenched in ice. The solution pH for all the cases
was found to be in the range of 4 – 5. Transmission electron microscopy (TEM) was carried out
at 200KV on samples prepared by dropping aliquots of the obtained colloidal solution on a
‘holey’ carbon coated copper grid, and subsequent drying in ambient temperature, with a JEOL-
JEN2010. Optical absorption spectroscopy was done with a dual beam spectrophotometer
(ELICO-SL164) operating between 350 – 1000 nm range.
Preparing dry powder for FTIR and X-ray analysis: Larger volumes (250 ml) of colloidal gold
nanoparticles were synthesized to ensure sufficient solid product, while maintaining similar
precursor molar ratio as explained above. The obtained colloidal suspension was placed in a
freezing chamber to de-stabilize nanoparticles leading to their flocculation. The sediment was
separated by centrifuging (4000 rpm) and was repeatedly washed with water and acetone (for X-
Ray diffraction studies only) to remove excess organic salts from the nanoparticle surfaces. The
washed powder was collected and dried on a Si (111) wafer for X-Ray analysis (Siemens D5000,
Cu–Kα radiation (λ = 1.54 Å) at a scanning rate of 3s/degree (2 θ) within the range of 35 – 85
degrees (2 θ)). In separate experiments, the washed powder was collected and compressed with
potassium bromide to form a pellet which was used in the transmission mode for FTIR (Perkin
Elmer Spectrum one) spectroscopy.

RESULTS AND DISCUSSIONS

Gold colloids are known to absorb specific band of light (with peak absorption wavelength
around 520 nm to 540 nm) due to surface plasmon resonance (SPR). The width of the absorption
band and the position of the maximum absorption peak depend on the morphology of the
particles (size, shape and uniformity), coagulation among the particles, and also the dielectric
environment [1,3,8,9]. Gold colloids studied here are stable for prolonged periods (over several
months to a year), thus coagulation and also the changes in their dielectric environment can be
neglected in our case. Hence all changes in the absorption spectra due to the synthesis conditions
can be attributed to variation in particle morphology. A comparison of the peak of the absorption
spectra of the colloids (Fig. 1a) show a red-shift in the absorption peak with decreasing molar
ratio from 6.5 until a ratio of 3 due to a nominal increase in particle size and an increase in the
number of non-spherical particles (as observed TEM of the nanoparticles, described in details
later). A blue shift was observed in the peak absorption wavelength for the gold colloid
synthesized with a precursor molar ratio smaller than three as shown in figure 1a. This can be
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Figure 1. Optical absorption of the gold colloids for various conditions. (a) Peak absorption
wavelengths of glutamate stabilized gold colloids for the studied ranges of precursor molar ratio;
(b) Increase of the plasmon absorption maxima at various intervals of time for precursor molar
ratios 7, 5, 3, and 2.
observed as a discontinuity in the plot of peak absorption wavelengths of the colloids around
molar ratio 3.
The increases in peak plasmon absorption intensities (Fig.1b) at various stages of particle
growth are notably different in case of syntheses with a molar ratio less than 3. The rise in peak
absorption (Fig. 1b), corresponding to the progress of the reduction process, indicates that at
relatively high concentrations of monosodium glutamate, the complete process of nucleation and
growth of nanoparticles is extremely fast (Extrapolating from the plot, the reaction starts at 40 s,
62 s, and 75 s respectively for molar ratios 7, 5, and 3, and the rise in the peak absorption
intensity for all the three cases has a slope of ~ 0.007). However, during the synthesis of gold
colloids with precursor molar ratio 2, the reaction is significantly delayed (reaction starts after
131 s) and is much slower (slope ~ 0.003, see figure 1b). From the observed similarity in the
reaction parameters for molar ratio higher than 3 and the discontinuities observed at precursor
molar ratio of 3 we logically conclude that a minimum of three glutamate ions are needed to
reduce one Au3+. Based on this stiochiometry, a scheme for the reaction is proposed:
°C
HAuCl 4 + ( x + 3) NaC 4 H 8 O4 N ⎯100
⎯⎯ → Au 3[C 4 H 8 O4 N ]− + 3 NaCl + HCl + x[C 4 H 8 O4 N ]− + xNa +
---- (1)
where (x+3) implies molar ratio of monosodium glutamate to chloroauric acid.

From transmission electron microscopy it was observed that similar to the conventional
trisodium citrate reduction process (Turkevich process) [6,8], the particle sizes in the colloids
synthesized with monosodium glutamate also depend on the concentration of the reducing agent
employed during the synthesis (Fig. 2a). It was found that the average diameter of the colloidal
gold nanoparticles and the number of non-spherical gold particles increased with the decrease in
the concentration of monosodium glutamate (Fig. 2). Average diameter of the nanoparticles
varied from 14.5 nm to 24 nm for a molar ratio (MR) of monosodium glutamate to chloroauric
acid kept between 10 and 2. The size distribution of the obtained nanoparticles were found to be
nominally wider (σ = 14 – 20 %) than what is reported for the most optimum trisodium citrate
reduction process (σ = ~15 % [6]).
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Figure 2 (a) Variation of particle size with the precursor molar ratio (MR); (b), (c), and (d) TEM
micrograph of nanoparticles synthesized with molar ratios 7, 5, and 3.
The appearance of non-spherical particles in the colloidal solution was found to be inversely
dependant on the concentration of monosodium glutamate in the reaction mixture. Though over
50 % of the nanoparticles in all cases were found to be fairly spherical (with aspect ratio of 1.1),
it was observed that the occurrences of larger aspect ratio particles became common only when
low concentrations of monosodium glutamate were used to reduce chloroauric acid (Fig.3a).
MR-7 colloids (high concentration of MSG), were found to have 90 % of the particles with
an aspect ratio less than 1.1, while in case of MR-2 colloids (lowest concentration studied), only
52 % of the nanoparticles were found to have an aspect ratio less than 1.1.
The formation of anisotropic gold nanoparticles for lower concentration of MSG with respect
to chloroauric acid in the starting solution can be attributed to the reduction in the concentration
of counter ions (Na+) at lower molar ratio synthesis process. The diffuse layer of the electric
double layer that stabilizes the nanoparticles, is known to have a high concentration of Na+ to
balance the strongly negative stern layer of adsorbed citrate ions in the Turkevich process or in
this case glutamate ions [6]. During the growth of a nanoparticle, a sufficient concentration of
Na+ ions in the diffuse layer ensures a complete surface coverage that would serve to control the
diffusion of gold ions onto the growing nanocrystals. This leads to a nearly isotropic growth as
commonly observed for the synthesis of spherical gold nanoparticles by trisodium citrate
reduction. Incomplete surface coverage due to lower Na+ concentrations (in case of synthesis
with low precursor molar ratios, and also in these experiments, where the reducing agent supplies
one Na+ ion per molecule) would lead to anisotropic diffusion of the Au3+ leading to the
formation of non-spherical nanoparticles.
Further experiments are being conducted to test this hypothesis by providing external source
of Na+ ions during the nucleation stages, which will be reported elsewhere. Preliminary results
by employing NaOH as the external source of Na+ ions in the starting solution show a marked
narrowing of the size distribution of the synthesized gold nanoparticles.
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Figure 3 (a) Comparison of the aspect ratios of the obtained colloidal nanoparticles with various
molar ratios of the precursors(MR implies the molar ratio of the precursors); (b) A typical FTIR
spectrum of glutamate stabilized gold nanoparticles, synthesized with a molar ratio of 7.
The presence of glutamate moiety on the nanoparticle surfaces was confirmed by FTIR
spectroscopy, by comparing the absorption peaks in the spectra of the colloidal nanoparticles,
with available IR absorbance data of monosodium glutamate from the chemical suppliers [10].
A typical FTIR spectrum of the glutamate stabilized gold nanoparticles (for molar ratio 7) is
shown in Figure 3b, which is similar for all other synthesized particles, shows strong absorption
at 1405 cm-1 which is a characteristic stretching vibration of the N – H bond in the amino acid.
Other absorption peaks in the obtained FTIR spectrum matching with the data from the chemical
supplier have also been marked in the figure.
Gold nanoparticles obtained by the glutamate reduction technique were found to be highly
crystalline. Typical X-ray diffractogram of glutamate stabilized gold nanoparticles is shown in
figure 4a. The width of the most intense peak ((111) peak at 2θ = 38.2 degrees) was employed to
calculate the average crystallite sizes of the nanoparticulate samples using the Debye Scherer
equation. It was found that for all molar ratios the average crystallite sizes matched fairly well
with the particle sizes obtained from TEM analysis in figure 2a (Fig. 4b).
In comparison, X-Ray diffraction analysis of gold nanoparticles synthesized with trisodium

Figure 4 (a) Typical X-ray diffractogram of gold nanoparticles synthesized with a precursor molar
ratio of 7 (b) A comparison of the crystallite sizes determined from the X-Ray diffractogram, with
the particle sizes obtained from TEM analysis (Fig 2a) for monosodium glutamate (MSG) and
trisodium citrate (TSC). Particle sizes for TSC were obtained from the literature [11].
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citrate (molar ratio 7, 4, 2, and 1) indicated that the nanoparticles had a highly agglomerated
structure. The sizes of the colloidal nanoparticles synthesized by employing trisodium citrate
obtained from the literature [11] was found to be in the order of two times the crystallite sizes as
determined from the diffractogram, employing the Debye Scherer equation. A more detailed
study on this aspect will be reported elsewhere.

CONCLUSIONS

We report for the first time a simple aqueous precipitation process to synthesize amine
functionalized gold nanoparticles by the reduction of chloroauric acid by monosodium
glutamate. The obtained spherical colloidal particles were comparable in size and shape to the
gold nanoparticles synthesized by the reduction of chloroauric acid by trisodium citrate in water.
Single crystalline gold nanoparticles can be obtained by this synthetic route which was
corroborated with TEM and X-Ray diffraction analysis. The particle size and anisotropy can be
controlled by the varying molar ratio of the reactants in the starting solution. At molar ratios of
monosodium glutamate, comparable or less than three times the number of free gold ions in the
reacting solution leads to the formation of anisotropic nanoparticles. That is attributed to arise
due to the incomplete coverage of the growing gold nanoparticles with sodium ions in the diffuse
layer of the double layer. Further experiments are being carried out to prove this hypothesis,
which will be reported elsewhere.

ACKNOWLEDGEMENTS

The authors would like to thank the Swedish International Development Agency (SIDA) for
financial support, and Prof. J. G. Hilborn for discussions.

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